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Spontaneous Formation of a Doubly Interlocking [2] Catenane Using Copper (I) and Palladium (II) as Templating and Assembling Centers

使用铜 (I) 和钯 (II) 作为模板和组装中心自发形成双联锁 [2] 链烷

基本信息

批准号：
10044104
负责人：
FUJITA Makoto
金额：
$ 2.24万
依托单位：
Nagoya University (1999)Okazaki National Research Institutes (1998)
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B).
财政年份：
1998
资助国家：
日本
起止时间：
1998 至 1999
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10044104/
关键词：
Self-assembly Catenane Template Palladium ESI-MS Phenanthroline 内部連結構造キラリティー電気化学

项目摘要

Doubly interlocking catenanes are chiral and complex topologies which have only been described recently. Our approach is to combine the two methods, based on coordination chemistry, which are termed as "template" and "self-assembly" strategies. In the template strategy, copper(I) complexes have been used as precursors, affording simple to topologically very complex catenanes.On the other hand, the self-assembly process furnishes in one chemical step sophisticated structures, including interlocking rings, from very simple molecular fragments and under mild conditions. A new method based on these two strategies has been used to construct a 4-crossing [2]catenane. The ligand used contains a central 1, 10-phenanthroline site attached to two pendent/4-pyridyl groups. The central site is used to complex a copper(I) center whereas the lateral pyridine groups are coordinated to palladium(II). The stepwise complexation procedure is virtually quantitative. It can be carried out both ways (copper(I) followed by palladium(II) or reverse) : The final complex is a chiral species incorporating 4 ligands, 2 copper(I) and 4 palladium(II) centers. It has been characterized in solution and its structure has been evidenced by ESI-MS.

双互锁链烷是手性和复杂的拓扑结构，直到最近才被描述。我们的方法是将这两种方法结合起来，基于配位化学，这两种方法被称为“模板”和“自组装”策略。在模板策略中，铜(I)络合物被用作前体，提供了简单到拓扑非常复杂的链环。另一方面，自组装过程在一步化学步骤中提供了复杂的结构，包括互锁环，从非常简单的分子片段开始，在温和的条件下。基于这两种策略的一种新方法被用来构造4-交叉[2]链环。所使用的配体含有一个中心1，10-邻菲咯啉中心连接到两个侧基/4-吡啶基团上。中心位置用于配位铜(I)中心，而侧位吡啶基团配位于钯(II)。逐步络合过程实际上是定量的。它可以通过两种方式进行(铜(I)，然后是钯(II)或反向)：最终的络合物是包含4个配体、2个铜(I)和4个钯(II)中心的手性物种。对其溶液进行了表征，并用电喷雾质谱联用确证了其结构。